Proceedings of the 7th lntemational Conference on

Properties and Applications of Dielectric Materials

lune 1-5 2003 Nagoya s11-1

Furanic Compounds in Dielectric Liquid Samples:

Review and Update of Diagnostic Interpretation and Estimation of hulation Ageing

R. D. Stebbins, D. S. Myers, and A. B. Shkolnik

S . D. Myers, Inc.
180 South Avenue
Tallmadge, OH 44278 USA
* E-mail: Randy.Stebbins@sdmyers.com .

ABSTRACT strength or degree of polymerization of 200. .When

Commercial laboratories and electrical equipment
owners have used analysis of furanic compounds in
dielectric liquids for more than ten years to evaluate the
continuing operation of transformers and to estimate
the degree of ageing of solid insulation. "be solid
insulation of transformers is comprised mainly of Kraft
paper. As the paper ages, the cellulose polymer
chains break down into shorter lengths with a
corresponding decrease in both tensile strength and
degree of polymerization. Further, the paper
breakdown is accompanied by an increase in the
content of various furanic compounds in the dielectric
liquid. Analysis for furanic compounds allows the
laboratory or the owner to make a determination as to
whether the breakdown of the paper .is an active
condition. It M e r allows a determination as to the
relative degree of the paper breakdown that bas
occurred. This paper reviews the tools that have
evolved to help perform these interpretations and
presents a system. to aid in the assessment of
transformer insulation ageing.
BACKGROUND
Kraft paper is widely used as solid insulation in
e l e c ~ c a l equipment, including pansformers [ 1.21.
Paper fibers are composed of cellulose, a nahU;llly
occurring polymer. Cyclical glucose monomer
molecules are bonded together by glycosidic bonds to
form cellulose. "be average length of the cellulose
polymer, measured as the average number of glucose
monomers in the polymer chins, is referred to as
degree of polymerization, usually abbreviated as DP.
This can be inferred directly by means of chemical
analysis. One such method for determining degree of
polymerization is ASTM Method D4243 [3].
The mechanical strength of the paper is the determining
factor for assessing remaining life of the equipment.
The IEEE Guide for Loading Mineral Oil Immersed
Transformers (IEEE Standard C57.91-1995)[4]
provides two widely used defmitions for end-of-life of
!"former solid insulation - 25% retention of tensile
the paper has aged addegraded to this point, it no
longer retains the capability of recovering from the
mechanical stresses one expects to encounter in a
normally operated transformer. Transient short circuit
conditions, switching. surges, and load fluctuations
cause mechanical movement in the paper Mapped
windings. Once paper bas weakened to the point
represented by these defdtions of end-of-life, it can no
longer be relied upon 'to tolerate these conditions
without rupturing.
, .
Direct testing of the solid h i l a t i o n for tensile strength
or degree of polymerization is very difficult.
Representative paper samples cannot be secured while
the equipment is energized.' Also, there is
considerable concem whether paper samples can truly
be considered to be representative, given the difficulty
in actually getting winding insulation from deep within
the coil assembly.
When the cellulose polymer chain breaks down, each
splitting of the chain liberates a glucose monomer unit
that undergoes further chemical reaction and becomes
one of a family of derivatives of 2-furaldehyde. These
derivatives, collectively known as h a n k compounds,
are partially soluble in oil [5]. Once formed, they
partition between the solid insulation and the oil phase
[6] and can be .determined through analytical test
methods [7,8].
The practical solution is to' obtain an oil sample and
analyze the sample- for liuanic compounds.
Representative oil samples are easily obtained
according to standard ASTM [9] and IEC methods,
usually even without the need to deenergize the
equipment. Sample analysis for furanic compounds
can be performed using high performance liquid
chromatography according to ASTM Method D5837
[7] or IEC 61 198 [8].
It is possible to analyze for a number of these furanic
compounds. Most often, laboratories determine the
concentration parts per billion (either by weight -
pgikg - or weight per volume pgL) of five furanic
compounds [5,6,7,8]:,

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2-furaldehyde (2FAL)
5-methyl-2-furaldehyde(5M2F)
5-hydroxymethyl-2-furaldehyde (5H2F)
2-acetyl furan (2ACF)
2-furfurylalcohol (2FOL)
Laboratory experimentation and field experience with
furanic compounds in transformers has shown that all
of these compounds except ZFAL are not very stable
under operating conditions found in transformers [9,10].
These compounds apparently form- and then further
degrade to 2FAL over a time span of a’few months.
2FAL is apparently stable for several years under the
same conditions.
INTERPRETING FURAN RESULTS:
Furan analysis can be performed on all dielectric
liquids used as insulating media in. power transformers.
In as yet unpublished work, S . D.Myers, Inc. has found
the following distribution of the five furanic
compounds in several years worth of furan data:
Table 1
Relative Abundance of Five Fu+c Compounds
than these results indicate. A possible answer can be
found in the work done by Grift%& Lewand, and
Pahlavanpour [IO] who determined that ZFOL is the
most susceptible of the furanic compounds to further
degradation and decomposition. The conclusion
drawn in our interpretations of furanic results is that the
ZFOL does form more frequently than the population
study would indicate. However, a disproportionately
larger hction of those results change, eliminating the
2FOL, prior to the analysis of in-service oil samples for
tiuanic compounds.
The fmt key point of interpreting furan analysis is
easily stated
y a profile of furanic compounds in dielectric
liquid samples indicates the presence offiranic
compounds other than 2-furaldehyde, this is a
strong indication that the condition causing
these furanic compounds to be generated is an
-
active condition.
In other words, paper in the transformer was degrading
or ageing abnormally at the time the sample was drawn,
or it had been degrading or ageing abnormally within a
few months earlier, at most.

% of All Please note that the converse statement - presence of

Conbound Data Sets ZFAL only is an indication that there is no active
condition - cannot be made. 2FAL will form from
5H2F 2.8 mild overheating, without other furanic compounds
2FOL 1.o being generated. Further, all conditions involving
ZFAL ’ ... 98.7 degradation of the paper in the presence of moisture
ZACF 1.2 may not generate measurable 2FOL.
, 5M2F 8.3
One test for furans may then tell an important part of
Further, experience in observing changes in furanic
the story. However, that story will not be totally
compounds profiles over time in the presence of known complete. A much better and more thorough
conditions ‘has lead to . the following conclusions interpretation of the data and diagnosis of any
regarding the causes of specific furanic compounds in suspected problem or operating condition may be
operating transformers: obtained by comparing current test results to past
history. This allows a clearer idea of the rate at which
: Table2 .. . furanic compounds are being generated. Clearly, any
Causes of Specific Furanic Compounds known generation of fiuanic compounds between the
dates that samples are drawn ixidicates a continuing
Comuound Observed Cause: .’
ageing and degradation of the solid insulation. The
5H2F Oxidation. degree of the problem can be evaluated from the
ZFOL High moisture relative rate of furanic compounds formation.
ZFAL General overheating or ’

’ Normal Ageing There are two remaining pieces to the furanic

ZACF Rare, causes not fully defmed
5M2F High temperatures
’
Of the “frequency of occurrence” data reported in
Table I, only one item is surprising - the relatively low
frequency at which 2FOL has been found. Cross
referencing furan data with moisture data [5] would
lead to a conclusion that there should be a much higher
incidence of moisture degradation of solid insulation
compounds interpretation “puzzle” with which this
paper will need to deal. At what content of furans
should an owier become concemed and either reduce
the interval between sanpiles for purposes of more
closely monitoring furanic cOmpounds or take
corrective action? What quantitative method uses
furan analysis to evaluate the rate and degree of ageing
of the transformer’s solid insulation system?

- 922.-
The paper will examine both of these questions. The % Life by Mean DP was calculated using the average
answer to the first depends to a large extent to the measured DP..(Table 4 includes the values from
answer for the second, so the second question will be different sectiok of the transformers that go into this
exanuned first. calculation), compared to an initial value of 1200 and
n 200. For example: . .
end oflife d e f ~ t i o of ..
QUANTITATIVE EVALUATION OF FURAN
ANALYSIS RESULTS . (1) Calculation of % Life Used by DP

There have been two general, quantitative methods % Life Used = {( 1200 - 263)/1000] X 100 = 93.7%
used to interpret furan results in terms of remaining life
of the solid insulation. In one method, results are Table 4
compared to all results from a population of operating Summary of DP Measurements
equipment using a .statistical. model to assign a
percentile score [6]. In a number of variations on the &
&
l.g ' -
Unit1 -
unit2 -
unit3
other method, either the 2-furaldehyde content or the
Winding A Top 220 254 38 1
total content of furanic compounds is used to calculate
Winding A Middle .290 351 404
a predicted degree of polymerization. Sbkolnik,
Winding A Bottom ' 321 291 , 407.
Bilgin, and Kelly [ 1 I] summarized some of these DP
Winding B Top 243 429 464
calculation methods and provided a bibliography of
Winding B Middle 306 445 45 1
papers for m e r study.
WindingBBottom 282 ' 390 Missing
WindingCTop ' 210 348 ~'401
Percentile Score Approach:
Winding C Middle 258 : 302 405
WindingCBottom ~ 234 . . 363 460
The percentile approach is very simple. In this
method, as large a database population of similar . Average '1 263 353. 422
transformers a s possible is assembled and the
population values for total furanic compounds are In the example above, the % Life Used was overstated
charted. A total furanic compounds result can then be by furanic compounds analysis compared to DP
plotted against this distribution, and it is possible to measurement by 1.4%, 7.8%. and 3.1%, respectively.
calculate the percentage of the overall population of This was fairly typical. It was also acceptable to be
similar units in the database that fall both below and biased in this.direction, as the difference was almost
above this value. For several years, S. D. Myers, Inc. always conservative. By overstating life used in this
used this method with significantsuccess. fashion, interpretations were biased toward preventing
unplanned or unscheduled outages.
At the time that this method was being pursued, S ; D. .. ;

Myers, Inc. had the opportunity on several occasions to
compare values for Percent Life Used, figured as above,
to an average of measured DP. This was possible to
achieve by measuring h a n i c compounds content .of
in-service transformer that were soon thereafter brought
into the S . D. Myers, Inc. facility for either disposal or
repaidremanufacture. The following table lists some
fairly typical values:
Table 3
Comparison of Actuarial Life Remaining
to Life Remaining Calculated by DP
A linear relationship for DP versus remaining life,
based on initial DP of ,1200 is not completely
appropriate, even though this is still widely used. A
further investigation of~themethod almindicates it was
much more severely biased than initially believed. It
is no longer considered to be a valid method of using
furanic compounds results to assess .insulation ageing.
The most charitable comment about the method is that
it did lead certain researchers to continue pursuing a
correlation of furanic compounds content to remaining
life when the methods of calculating DP from furans
became controversial. . .
'

. .
w -
Unit 3 Predicting DP Approach:
Mean DP 263 353 422
. . , ,
. , Researchers developed equations to relate furan
% Life
concentrationh oil with degree of polymerization for
Usedby ' 93.7% ' 84.7% ' 77.8%
the paper in transformers [11,12,13]. Initially, such
Mean DP
determinations provided good apparent correlation of
F u r a n s ~ ~ b 854
' 491 ' l,23
DP to either total furan content pr content of 2FAL.
% Life
Data points were obtained by analyzing oil samples for
Used by 95.1% 92.5% 80.9% furanic compounds testing then obtaining paper
Furan~ob .
samples. from either a field inspection or tear down of
the transformer from-which the oil had been drawn.

- 923
As more data were obtained, the direct correlations
upon which these calculations were based were found
in many cases to be less than completely reliable [ 131.
Effect of Thermallv UDeraded Paper: During the
industry discussion that arose as more data were
gathered concerning whether furanic compounds
analysis was huly useful to predict DP and remaining
life, the position of the S.D. Myers, Inc. laboratory was
that there had to be a reasonable correlation. In
investigating the situation, the S . D. Myers, Inc.
laboratory determined that transformers from which the
statistical database results had been drawn differed
from the early furanic compounds to DP calculation
studies. Further, transformers contributing ,additional
data points to the evolving studies of DP and furan
compounds differed from the transformers from which
the earliest data points were drawn.
Most of the transformers in the actuarial database were
manufactured in North-America, subsequent to 1960,
and were 65 degree C rise units. This turned out to be
an important criterion for interpreting furan results 1141.
A review of the earlier studies to arrive at a calculated
or predicted DP reveals that most transformers
contributing data to those studies were largely units
manufactured outside'of North America. Further, data
that seemingly called the earlier studies into question
appeared to arise from a mixture of post-1960
transformers with units manufactured earlier in North
America and with'units manufactured outside of North
America. . .
..
While it is not a f m rule, most 65. degree C rise
transformers manufactured in North America since
approximately 1960 used'thermally upgraded paper in
their solid insulation system Commonly, thermal
upgrading of the paper was accomplished by
impregnating the paper with dicyandiamide (dicy).
Bilgin, Sbkohuk, and Kelly [I41 compared fi"
formation from ageing of thermally upgraded paper and
paper that had not been thermally upgraded. They
also examined the stability of furanic compounds in oil
spiked with dicyandiamide.: Finally, a review of
furanic compounds concentrations in-two populations
was undertaken. One population was primarily
'
transformers that were manufactured with thermally
upgraded paper. The other was transformers without:
thermally upgraded paper.
..
The conclusions were: (1) that thermally upgraded
paper generated substantially lower furanic compounds
concentrations, (2) that furanic compounds
demonstrated .lower stability in insulating liquids
spiked with dicyandiamide, and (3) that the population
studies confirmed the 'conclusions of the laboratory
work. Furanic .compounds, on average, were
substantially higher in operating transformers that were
- 924
not manufactured using thermally upgraded paper.
Predicting DP for Two Transformer Pooulations:
This work [14] and subsequent work by the same
researchers [I I] allowed them to derive a preliminary
model for predicting DP from furanic compounds
content, separating the two populations of transformers
based on whether thermally upgraded paper had been
used in manufacture of the equipment. They found
that a model and an equation from a prior study [I51
was the most reasonable approximation for DP in
transformers without thermally upgraded paper based
on the level of furanic compounds that were found in
operating transformers. A number of laboratories use
this technique and refer to it as the "Chendong
Equation".
While apparently adequate for transformers without
thermally upgraded paper, correlation is not good when
the Chendong equation is applied to data from
transformers with thermally upgraded paper. The
other model, developed specifically for transformers
with thermally upgraded paper, also was based on
2FAL when published [I I]. Unpublished studies
since have updated this model. The revision is
published here for the fust time,although it has been
distributed to individuals and standards organizations
for verification and comment.
Revision of the DP Calculation Model:
Although the initial model was based on ZFAL,
subsequent work indicates a better correlation is
obtained if the total furanic compounds content is used
to predict degree of polymerization.
The equation and prediction techniques in this paper
are based on furanic compounds conient expressed as
p a r 0 per billion by weight (pgkg). The equations
must be modified io address parts per billion, weight io
volume (&L), or other units.
The revised equation becomes:
(2) Predicted DP from Total Furanic Compounds for
Transformers with Thermally Upgraded Paper
DP = [loglo(total furans) - 4.03551 I-0.002908
A modification of the Chendong equation for
transformers without thermally upgraded paper, using
2FAL.content in ppb by weight (pgkg) becomes:
(3) Predicted DP from 2FAL Content for Transformers
without Thermally Upgraded Paper
DP = [loglo(2FAL X 0.88) - 4.511 / -0.0035
Finally, as mentioned earlier, use of a linear
relationship between life remaining or life used and DP,
with a “beginning of life” value for DP of 1200 is not
completely appropriate. New paper before being
installed in a transformer typically has a degree of
polymerization of 1200 to 1400. After factory drying
and assembly, our experience is that .new paper in a
new transformer has a DP of 800 to 1200, and It is
usually more appropriate to figure life assessment
based on changes from the lower limit of this range.
Simply substitutingthe value for starting DP of 800 for
1200 in the linear equation above (Equation I) is not an
adequate method for determining life used or life
remaining. A more appropriate method is to calculate
the predicted DP for the transformer using the more
appropriate of the two equations above (Equation 2 and
Equation 3) and then to use the following to estimate %
Life Used [16].
(4) % Life Used from DP
% Life Used = [log,, (DP) - 2.9031 I-0.006021
The initial ageing rate of paper, relative to a decrease in
DP, is more rapid in the early stages. The first third
of transformer paper’s effective life shows a decrease
in DP from a starting point of 800 to 504 - a decline in.
DP of 296. The fmal third of the paper’s life
experiences only a decline from 317 to an end-point of
200 - a decline of only 117. , . .
. .
From this calculation, many laboratories express the
furan and calculated DP in term of Life Used. .
SUMMARY AND CONCLUSION :
. .
Interpreting Fnranic Compounds Results:
Loss of life can then be taken &to consideration when
making interpretations of furanic compounds test data.
Consider two sets of such data, as fust samples from
operating equipment. Both are all ZFAL, and the
results are 100 ppb and 250 ppb, respectively.
Applying Equation 2, Equation 3, and Equation 4 to
these data yields the following calculated results:
Table 4
Some Calculated DP and Life Used Results
with Thermally without Thermally
Upgraded Paper Upgraded Paper
m -
DP %Life Dp % Life
-
Used used
9.6% . 786 1.3%
lOOppb 700
250ppb 563 25.3% 686 11.1%
At 100 ppb, minimal damage has been done to the solid
insulation. Unless the transformer is nearly brand new,
there is no reason to expect that there is any sort of
active condition generating additional furans.. Only
normal monitoring and testing to establish a trend of
results would be recommended. For most equipment,
this would mean annual retesting of the furan content.
At 250 ppb,’DP has declined substantially. It is
important to determine whether an active condition
exists that’is prematurely ageing the solid insulation. A
shorter retesting interval ivindicated, and the actual age
of the equipment, size of the unit,and critical nature of
the application are all factors that must be considered.
In most cases, a retest interCal of three months to six
months would be appropriate for a fust test yielding
this !&d of result.
It is beyond the scope.of this paper to review all the
possibilities and intelpretations for furanic compounds
results. As a brief summary of some of the important
points to consider: , .
,
I . The total level of furans is considered:
2. The presence of compounds other tban ZEAL is
given greater weight.
3. Trends in &ta are more important than the
absolute value of the €uranic compounds results.
This is the only real way to identify whether, .
a
profile truly indicates an actiye condition.
4. The age, nmiufacture, and,insulation class of the
. transformer must be considered.
5. Size of the ;lit, application type, and critical
nature of thk application help to determine the
appropriate .interval for retesting.
6. Other testing such as dissolved gas analysis and
moisture analysis is extremkly useful in properly
interpreting €uranic compounds results.
7. Oil maintenance will decrease the furancontent
and this mu$ be taken @to account -for life
assessment.
There are several valuable uses for these data and these
interpretations. Some of these are:
Active overheating and ageing of the solid
insulation reduces, equipment life., Proper
maintenance and changes in operating conditions
can be instituted to extend equipment life and
maximize the use of valuable assets.
Life assessment using furanic conipounds data
can be used to prioritize equipment for removal
and replacement. -An example is that furanic
compounds data have been obtained for a number
of Askarel filled transfohrs in an industrial
plant. The relative age of the equipment as
determined by these results was used to determine
how &y and which units would be replaced
over the course of a “Iti-ye% budgeted project.
Furanic compounds results can be used as a
- 925 -
 consideration in ‘a .preventative maintenance provide information on the progress of these projects.
program.. -Very high furanic compound results
may indicate -&at preventative oil maintenance is REFERENCES:
not a cost effective option. Replacement or
remanufacture may be a better solution. [l] M. Homing, J. Kelly, S. Myers; “Transformer
4, .An estimate of ageing gives an approximation Maintenance Guide”; Transformer Maintenance
concerning replacement of the equipment. For Institute, Div. S. D.Myers, Inc.; 2001.
example, a: ten year !old transformer thst bas [2] S. D. Myers, J. J. Kelly, R. H. Parrish; “A Guide to
thermally upgraded paper with 745 ppb of total Transformer Maintenance”; Transformer Maintenance
furans is approximately halfway ~througb its Institute, Div. S. D. Myers, Inc.; 1981.
expected life. The owner may tentativelyplan to [3] ASTM International, Committee D9; “D4243
.replace it in approximately another ten years. Standard Method for Measurement of Average
Viscometric Degree of Polymerization of New and
As an aid in interpreting furanic compounds results, the Aged Electrical Papers and Boards”, 1999.
following table is provided (ppb by weight, pgkg):’ [4] IEEE; “Standard C57.91 Guide for Loading
Mineral Oil Immersed Transformers”; 1995. . .
Table 5 [5] D. P. Myers, J. R. Sans; “Field Studies of Furan
Calculated DP and Life Used for a Range of Furanic Formation in Transformer Liquids”, 59’ International
-Compounds Results Cod. OfDoble Clients; 1992.
[6] J. R. Sans, K. M. Bilgin, J. J. Kelly; “Large Scale
Without With Survey of Furanic Compounds in Operating
Thermally Thermally Transformers”; 1998 IEEE International Symposium
Upgraded Upgraded ’ ..
’ . , on Electrical Insulation; 1998.
Paper Paper .’ ’ I . 4 . ’. [7] ASTM International, Committee D27; “D5837
ZFAL Total ‘Calculated . %Life Standard Test Method for Furanic Compounds in
!a&-! !?I& Dp &.& Electrical Insulating Liquids by High-Performance
Liquid Chromatography (HPLC); 1999.
58 si 800 ’. . ,o [8] International EIecbotecbnical Commission;
130 * - 100 ,700 . . 10
“International Standard IEC 61 198,. Mineral Oils -
’

292 i95 600 ’’ 21

Methods for the determination of 2-fiufural and related
654 381 ~- , ~ 5 0 0
”
I. . 34 compounds”; 1993.
. . 1464 745 ’ 400‘ , ~ -50
[9] ASTM International, Committee D27; “D923
1720 852 380’ . . .... 54
Standard Practices for Sampling Electrical Insulating
2021 974 , .360-
. 58
, 2374 11-13 340 ’’ ”’’ - . 62
Liquids”, 1997. ~ .
[IO] P. J. G r i f f i L. R. Lewand, B. Pahlanvanpour;
2789 ,, 1273 , 320 1 . . 66
“Paper Degradation By-products Generated Under
3277 1455 ’ ’ 300 71
Incipient Fault Conditions”; 6 l YInternational Cod. Of
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4524 1902 260 ’. ,81
[ l l ] A. B. Shkolnik, K. M. Bilgin, J. J. Kelly;
5315 2175 ’ 240 a7
6245 2487 220 “Creating a Preliminary Model for Estimating Degree
93
of Polymerization”; 66’ International Cod. Of Doble
7337 2843. 200 100
Clients; 1999.
. ,
Ongoing R&D Activities: [12] P.-J. G r i f f i L. R. Lewand, E. Finnan, J. Barry;
“Measurement of Cellulosic Insulation Degradation”;
Additional data points are being added to &e general 60’ International Cod. Of Doble Clients; 1993.
population for predicting of DP. . .
[13] A. H. Cookson, C. M. Cooke; “Discussion
.. Meeting Summary for Group 15 (Materials for
Studies of oil oxidation and tekile strength reduction of Electrotechnology)”; Electra, October, 1998.
paper are being reproduced to incorporate. DP analysis [I41 K. M. Bilgih; A. B. Shkohk, 1. ‘3: Kelly; ‘The
for a better understanding of how oil oxidation products Effect of Dicyandiamide in Insulation on 2-furaldehyde
contribute to Kraft paper ageing.
- . Concentrations in ’ Transformer. Oil”; TechCon 99,
... 1999.
New :insulating fluids been, into the :in~odu;e~ [15] 1. Chendong; “Monitoring Paper Insulation Agin
by Measuring Furfural .Contents in Oil”; 7%
&arket. .Laboratory and field studies are being
International Symposium on High Voltage
performed concerning how the. ageing of these newer
fluids affects the ageing rite of the solid insulation. Engineering; 1991.
[I61 W.J. McNutt; “Section 9, Tutorial on Electrical
It is anticipated that’the presentation’of this paper will Grade Insulating , Papers”; 1993 Doble .. Client
Committee Fall Meetings; 1993.

926 -